Method of producing precipitates



Nov. l2, 1935. A. J. MYHREN ET AL 2,020,325

METHOD OF PRODUCING PRECIPITATES Y.

Filed Deo. 15, 195s -sawwfv [z/Ac may @fr a GAS @6) 27 ATTORNEYS Patented Nov. l2, 1935 UNITED STATES PATENT OFFICE METHOD F PRQDUCING PRECIPITATES Application December 15, 1933, lSerial No. 702,578

23 Claims. (Cl. 23-135) The present invention relates to the production of precipitates, and has for its object the provision of an improved method of producing precipitates by the reaction of a gas with a solution, for example by the reaction of carbon dioxide with limewater (solution of calcium hydroxide) to form a precipitate of calcium carbonate, or by the reaction of hydrogen sulfide with solutions of compounds capable of reacting with hydrogen sulfide gas to form a sulfide precipitate, for example, a

solution of zinc sulfate (which reacts with hydrogen sulfide as follows: ZnSO4+H2S=ZnS+H2SO4) or of cadmium sulfate (which reacts with hydrogen sulfide as follows: CdSO4+H2S= CdS-i-HzSOi) The invention more particularly contemplates the production of a zinc sulfide precipitate that can be worked up to zinc sulii-de pigment by aging, calcination, quenching in water etc. In a preferred embodiment of this application of the invention, zinc sulfate solution is brought into reaction with hydrogen sulfide gas by mixing in an eductor (preferably of the Venturi type) with repeated mixing'of the resulting slurry with hydrogen sulfide gas (also preferably in an eductor) under conditions insuring intimate contact of the slurry and gas. This preferred embodiment of the invention will be described herein, as an example.

Further objects of the invention in its application to the production of a zinc sulde precipitate are the provision of (1) A method for intimately mixing zinc sulfate solution with relatively large volumes of hydrogen sulfide gas by causing a current of zinc sulfate solution to entrain by suction, for example in Venturi tube eductors, hydrogen sulfide gas,

which is thereby brought into intimate contact with the zinc sulfate solution.

(2) A method by which zinc sulfate solution (or a slurry consisting of zinc suliide precipitate in suspension inan aqueous solution of zinc sulfate and sulfuric acid) is repeatedly brought into intimate contact with hydrogen sulde gas in the manner described in item l. y

(3) A method whereby hydrogen sulfide gas and zinc sulfatevsolution, or a slurry as described in item 2, are repeatedly recirculated in intimate contact, the hydrogen sulfide gas being entrained by suction bythe zinc sulfate solution or slurry in the manner described in item 1.

(4) A method whereby a current of hydrogen sulfide gas andv a current of zinc sulfate solution (or slurry) fiowing in general countercurrent are brought into intimate contact by the methods described in items 1, 2 and 3.

In the preferred practice of the invention the zinc sulfate solution and hydrogen sulfide gas are mixed in Venturi precipitators, that is to say 5 eductors of Venturi tube type, so constructed and y operated that the zinc sulfate solution is brought in the form of thin films into contact with relatively large volumes of hydrogen sulfide gas. The reaction between the hydrogen sulfide and the 10 zinc sulfate solution is facilitated and accelerated by the intimacy of contact so obtained. The limiting factor of the velocity of this reaction is the rate at which hydrogen sulfide is dissolved in the zinc sulfate solution. The greater the sur- 15 face of contactbetween hydrogen sulfide gas and zinc sulfate solution, the more rapidly Will the hydrogen sulfide dissolve in the Zinc sulfate solution.

Once the solution of hydrogen sulfide in the zinc sulfate solution has occurred, the formation` of 20 sulfideions occurs with great rapidity and the reaction of sulfide ions with the zinc ions already in the solution to form zinc suliide precipitate likewise occurs with great rapidity.

A further advantageous feature of the process 25 of the invention is that the precipitation is accelerated by keeping the zinc sulfate solution cool (at or near room temperature for example), hydrogen sulfide being more soluble in cold aqueous solutions than in hot aqueous solutions. 30

In this practice of the invention the Venturi precipitators discharge the zinc sulfate 'solution (or slurry) and hydrogen sulfide gas into tanks appropriately` closed so as tojretain the hydrogen sulfide gas. 35

The invention will be more readily understood from the following description taken in conjunction with the accompanying drawing, in which:

Fig. 1 is a diagrammatic elevation of a suitable apparatus for the practice of the invention. 40

Fig. 2 is a section on the line 2-2 of Fig. 1, showing in detail the construction of the Venturi tube eductor 6, 4and likewise of the eductors 6', 6",1, 1 and 1" in Fig. 1.

The apparatus illustrated in the drawing com- 45 prises three tanks 5, 5', 5" (arranged in series), of circular cross-section and with conical bottoms, each tank being provided with two Venturi tube eductors 6 and 1, B' and 1" and 6 and 1", re-

spectively. The series oftanks is provided with 50 a gas inlet pipe. 8 (entering the top portion of tank 5") and a gas outlet pipe9 (discharging from tank 5). A gas pipe 8 connects the top portions oftanks 5" vand 5' and a gas pipe 8 connects the top 'portions of tanks 5' and 5. The 55 system .of pipes 8", 8', 8 and 9 connects the tanks in series at points above the normal level (a) of liquid or slurry therein in such fashion that gas can flow freely through the series of tanks.

The gas outlet pipe 9 dips below the liquidlevel (b) in a water seal I0. The gas-space above the liquid-level (b) in the water seal I0 is connected by a pipe I I with the suction side of a fan I2. The pressure side of the fan I2 is connected by a pipe I3 with a screen-box I4, which contains metal screens (preferably vmade of a metal of high heat conductivity such as copper) set across the path of the gases therethrough. The screen box I 4 is connected by a pipe IB-to a gas burner I6. provided with a stack I1.

It is to be understood that the screen box Il and the burner I6 are oi particular utility when the gas utilized is combustible. In that case, the

. metal screens in the box Il prevent back-firing of the name in the -gas burner II. In case the gas used is not combustible, the screen box Il and the burner4 I6 may-be .dispensed with.v The water seal I0 is of utility not only as a further safe-guard against back-ming, but also as a means of regulating the effective suction of the fan l2. The eiective suction of the fan l2 on the outlet pipe l may be increased by lowering the water-level (b) inthe water seal ill, and decreased by raising the water level. Moreover, the water seal III prevents the entrance of air into the tank 5 whenthe fan |2 is shut down, for exampleV for the purpose of attaching a spare ian.

The tanks B, l' and 5" are provided with pumps for liquid and/or slurry transport, and pipe lines for -liquid or slurry are appropriately connected with the pumps, tanks and Venturi tube eductors in such fashion that liquid and/orslurry can be transported through the sexies of tanks and likewise partly recirculated in the inv dividu'ai tanks, while being brought into intimate contact with gas traversing the series of tanks in general counter-current with the liquid and/or slurry. Each of the six Venturi tub'e eductors (C, 1,1', 1', t" and 1) is arranged to recirculate gas through the tank with which it is operby discharging it into tank I. The Venturi tube eductors 1, 1' and 1" serve to recirculate liquid or slurry through the tanks with which they are connected (through tanks I, l and 5", respectively). 'I'he Venturi tube eductors l' and l" serve to convey liquid or slurry from one tank into the next tank in the series. Thus, Venturi tube eductor 6' serves to convey liquid or slurry (withdrawn from tank 5) into tank 5'; and Venturi tube eductor S" serves to convey liquid or slurry (withdrawn from tank 5') into tank I".

The apparatus shown in Fig. 1 will now be described in greater detail:

A pump 2l is connected on its suction side to a source of liquid (not shown). side,.the pump 20A is connected with a pipe 2|, part of which consists of the rubber hose segment 22, provided with a pinch valve 22. The pipe 2| leads to the Venturi tube eductor C. Between the pinch valve 22 and the eductor 6, the pipe 2| is provided with a pressure gauge 24, for indicating the rateof delivery of liquorto the Venturi tube eductor i.

-'I'he structure of the Venturi tube eductor 6 will be more clearly understood by reference to Fig. 2. 'Ihe pipe 2| connects with a duct 25,

On its pressiu'e in which is placed a spiral baille 2|. The duct 25 terminates in a discharge nozzle 21 in a gas chamber 2B, connected by a pipe 28 to the upper portion of the tank i (i. e., the portion oi the tank 5 above the line of normal slurry or liquid '5 level a therein). The nozzle 21 is placed concentrically with a Venturi tube 2B communicating with the gas-chamber 2l at a point opposite the nozzle.21.' v t Referring. again to Fig. l,4 the suction side 'oi 1o a pump I I is connected by'a pipe 32 to the discharge oriiice at the tip of the conical bottom of tank I. The pressure side of pump ll is connectedtoa pipe 33, dividing at its upper end into a branch pipe 24 leading back into the tank 5 l5 through the Venturi tube eductor 1, and into branch pipe 2|', leading into the Venturi tube eductor I. The branch pipe 34 is provided with the rubber hose segment I5, equipped with the pinch valve 26, and is also provided with the'20 pressure gauge 21, between the pinch valve It and the Venturi tube eductor 1. The branch pipe 2i' is likewise provided with a rubber hose section 22 equipped with a pinch valve 23', and

explained, by appropriate adjustment oi the pinch valves 28' and 8|, respectively; and that the relative amountsof liquid or slurry ilowing through the pipes 2|' and 3l can be determined at any time by comparing the reading of the a5 gauges 2l' and 21.

Thestructure of the Venturi tube eductors 16', 1, 1' etc. is the same asthat ofVenturi tube eductor l hereinbefore described. Pipes I9. I9 and Il" connect the upper portion of the tanks 40 l, l and l" with the gas chamber of the Venturi tube eductors 1, 1' and 1", respectively. y

` The structure and arrangement of the pump l I pip'es 32 and 23', branch pipe 3l' with the rubber-hose segment 3l', pinch valve 2t' `and gauge 45 31', branch pipe 2I" with the rubber hose segment 22", pinch valve 22" and gauge 2l", and the v Venturi tube eductors 1' and l", are the same with respect to tanks I and l" as the structure and arrangement ot the correspondingly identi- 50 ned element's'described with respect to tanks 5 and 5'.

The pump 3|" is connected on its suction side to the pipe 22" communicating with the discharge orice in the conical bottom of the tank 5". The 55 pressure side oi.' the pump 2|" is connected to the pipe 32", which divides hito the branch pipe 34" (connecting with the Venturi tube eductor 1) and branch pipe Il, which'serves as an outlet for the discharge of liquid or slurry from the system. 00 The branch pipe Il" is provided with the hose segment 25", having the pinch valve 20", and with the pressure, gauge 31". The discharge pipe Il 'is provided with a hose segment Il, equipped with a pinch valve Il. It will be understood that the relative amounts of liquid or slurry discharged through the pipe 3l and returned to the tank i" through the Venturi tube eductor 1" can be regulated by appropriate adjustment of the valves 4t 70 and 36", and that the amount of liquid or slurry entering the Venturi tube eductor 1" can be determined at any time by reading the gauge 31".

l The apparatus shown in the drawing is operated as follows for producing a zinc Vsulicle precipitate 75 solution: i Y

Hydrogen-suldeis vintroduced into the series of tanks through the inlet 8"., and circulated in succession through tank 5", pipe 8', tank 5', pipe 3, tank 5, outletvpipe 3 and water-seal I0 by the suction produced by the vfan I2. The effective suction of the fan I2 can be adjusted and regu-v lated by suitable adjustment of the water-level b in the water-seal I0. litl will be understood that the absorption of hydrogen'sulde by solution in,`

and reaction with, the zinc sulfate solution likewise tends to draw gas into the system through the pipe 8" by suction. The water-seal I0 prevents air from entering the system when the fan |2 lis shut down for any reason, as for example for the purpose of attaching a spare fan to the gas outlet line 9.

The fan I2 forces the gas through the line I3, the screen box Il and the line I5 to the gas burner I6. The products of combustion (e. g. sulfur dioxide) are removed from the burner I6 by the stack |1. Back-firing of ilame from the burner I6 into the system is guarded against by metal screens v(made of a metal of high heat conductivity, e. g. copper) placed in the path of the gases in screen-box I4. The water-seal II) is a further safeguard against back-firing.

Purified zinc sulfate solution is introduced (preferably continuously) into the system by pump 20, which delivers solution tothe Venturi tube eductor 6 through the pipe 2|; The amount of solution transported by the pump 20 through the pipe 2| can -be regulated by adjustment of the pinch valve 23 on the hose segment 22.` The rate of flow of solution into the Venturi tube eductor 6 is indicated by the pressure gauge 24, connected in the pipe line 2| at a point between the Venturi tube eductor and the pinch'valve 23.

From the pipe 2|, the solution enters the duct 25 of the Venturi tube eductor 6. A swirling moi tion is imparted to the solution flowing through the duct 25 by the spiral baille 26. The swirling stream of solution then passes through the nozzle 21 in the form of a conical expanding jet into the gas chamber 28. 'I'he jet traverses the gaschamber 28 and enters the Venturi tube 30, which is concentric and coaxial with the nozzle 21. In the Venturi tube 30, the velocity of the jet of solution is sumciently increased by the constriction of the Venturi tube to create suction in the gas chamber 28. Hydrogen sulfide gas is thus withdrawn from the gas-chamber 28 by the suction of the Venturi tube and by entrainment in the jet of solution. The suction in the gas-chamber 28 draws hydrogen sulfide gas through the pipe 29 into the gas-chamber `from the upper part of the tank 5. The Venturi tube 30 discharges this gas, together with a'slurry of zinc sulfide precipitate formed by reaction of the gas with the solution,

into the tank 5. The gas is brought into intimate Q contact with the solution in the form of thin films and small droplets in the Venturi tube 30 so that the reaction between hydrogen sulfide and zinc sulfate is initiated, with formation of a slurry of zinc sulfide, zinc sulfate and sulfuric acid soluorifice in the conical bottom of the tank through the pipe 32 -by the pump 3|, which forces the slurry through the pipe 33, into the branch pipes 34 and 2|'. The relative amounts of slurry ilowing into these two branch pipesare regulated by Ii appropriate adjustments of the pinch valves 38 and 23'; the pressure gauges 31 and '24', respectively, indicate the prevailing pressures and thus the rates o! ow in these .two branch pipes.. The slurryA entering the Venturi tube eductor 1 10 is mixed therein with hydrogen sulflde gas taken Vfrom the tank 5, and then returned to tank 5.

The Venturi tube eductor 1 functions with respect to mixing the gas and slurry in the same manner as the Venturi tube eductor 6. The slurry 15 entering the branch pipe 2|' passes into theVen-V turi tube eductor' 6',which functions in the same manner as Venturi tube eductor. 6, with respect to mixing the slurrywith gas (except that, as will be obvious from the figure, the Venturi tube 20 eductor 6'.- draws gas through its gas-pipe 29' from the tank 5'). The. Venturi tube eductor 6' discharges slurry into tank 5 and thus transports slurry from tank 5 to tank 5'; while the Venturi tube eductor 1 returns slurry to tank 5. .25

It will be understood that in order to secure a desirable uniform and constant iiow of slurry through the apparatus, the Venturi tube eductor B' must transfer to the tank 5' an amount of slurry corresponding to that entering-the tank 5 30 through the Venturi tubeA eductor 6. The rate of discharge of Venturi tube eductor 6' may be suitably controlledwith this object in view by appropriate adjustment of the pinch valves 3B and 23'.' 35 It'will also be understood that the capacity 'of the pump 3| must in consequence be adequate to pump all the slurry supplied to tank 5 by pump 2|) plus the amount of slurry returned to Y tank 5 by the Venturi tube eductor 1. 0

The slurry charged into tank 5 by the Venturi tube eductor 6' is recirculated in tank 5 through the Venturi tube eductor 1' and transported to tank 5" through the Venturi tube eductor 46" in a manner similar to that just de- 45 scribed.

Slurry is withdrawn from tank 5" by the pump 3| through the line 32", and pumped into the. line 33", whence it is in part discharged from the system through the line 38, and in part re- 50 turned to tank 5" through the Venturi tube eductor 1". The ratio of the amount discharged through the line 38 to that returned to tank 5" through Venturi tube eductor 1" is appropriately controlled by proper adjustment of the pinch valves 3B" and 40. -This adjustment is facilitated by the fact that the readings of pressure gauge 31"' are an indication of the rate at which slurry is suppliedto the Venturi tube eductor 1".

In order to secure uniform and continuous ilow of slurry through the system, it will in general be desirable to adjust the amount of slurry discharged from the outlet 38 so that it corresponds to the amount of slurry fed into the system through the'Venturi tube eductor 3.

In the practice of the invention in the appa- A ratus illustrated in the drawing, it will generally be advantageous to recireuate the slurry at a rate that is a multiple 'of the rate at which slurry is transferred from tank to tank; for example, the ratio of volume of slurry recirculated to volume of s'urry forwarded through the tanks may be 4to 1, in case a. zinc sulfate solution containing 30 grams .of zinc (Zn) per liter is used. For this purpose, it may be vadvantageous in such in apparatus to construct the recirculating Venturi tubeleductors 1, 1 and 1" larger than the transporting Venturi tube eductors 6, f and 6"; for example, the linear dimensions of 1, 1 and 1" may be twice those of 6, C and 8". In an apparatus having more than three tanks in sexies, the contemplated mixing eilect may be obtained with a ratio of recirculation to forwarding of less than 4 to 1, other conditions remaining the same.

In producing a zinc sulfide precipitate as here- Adepth of the conical bottom ofthe tank is 5'.

Eachtankisadaptedtocontainfrom 150 to200 gallons of zinc sul-fate solution or slurry of precipitated zinc sulfide in zinc sulfate and sulfiu'ic `acid solution, leaving ample room for an atmosphere of hydrogen suliide gasabove the liquid level. The Venturi tube eductors are so operated that the precipitator 6 is supplied with 20 gallons of zinc sulfate solution per minute and the transferring precipitators 6' and I" discharge corresponding amounts of slurry. 'Ihe volume oi.' feed entering the precipitators is controlled by ad- Justing the pinch valves in accordance with the pressure registered by the gauges in the downcomers leading to the precipitators. The recirculating precipitators 1,71 and 1" recirculate about 8O gallons of slurry per minute. Each Venturi tube eductor entrains from 25 to 50 volumes (or more) of gas containing at least 50% of hydrogen sulfide gas for each volume of liquor or slurry. The gas introduced into the apparatus (pipe 8") is substantially pure hydrogen sulide (about 99.5% HzS), and the exiting or spent gas (pipe 9) contains from 50 to 75% hydrogensulfide. The volume of exiting gas is of course very substantially smaller than the volume of gas introduced through pipe 8", in consequence of the precipitating reaction, and since the 'only gases (other than hydrogen sulfide) Aentering the apparatus are relatively very small amounts of air, the eiiiciency of hydrogen sulde consumption in the apparatus is about 99.5-98.5%. The zinc sulfate solution treated contains about 30 gramsZnperliteror about 'lgrams ZnSOiper liter. In this operation, with three tanks in series, the slurry is mixed with hydrogen sulfide gas in an eductor from ten to iifteen times before being discharged from the apparatus, and there is substantially no short-circuiting of -solution through the apparatus without adequate mixing with hydrogen sulilde gas. The slurry discharged through the outlet 38 contains about 1.5 grams unprecipitated Zn per liter, and about 4.5% sulfuric acid, 'I'he elimination of ZnSO4 in the crude slurry as discharged from the precipitating system is thus 95% approximately. During the subsequent aging treatment lasting several hours in which the crude zinc suliide precipi.

tate is maintained in Contact with the acid motherl liquor, the elimination of zinc sulfate is increased to about 98% by reaction of the residual zinc sulfate withhydrogen suliide gas adsorbed by the zinc s'ulfide particles and gradually desorbed during the aging.

The plant in question produces labout five n et tons zinc sulfide pigment per day. After aging treatment, the precipitate is separated from the mother liquor, dried, caleined and processed in a way similar to the nishing treatmentof litho- 5 pone.

We claim:`

1. The method of producing precipitates by the reaction of a gas with a solution which comprises passing the gas and the slurry that results l0 from the interaction of the gas and solution 'through a series of tanks, withdrawing from each tank in the series and returning thereto a certain amount of slurry intimately admixed with a considerably larger volume of gas withdrawn l5 from the tank, and withdrawing from the last ltank in the series an amount-of slurry substantially equivalent to the amount of solution introduced into the first tank in the series.

2. The method of producing precipitates by the reaction of a gas with a solution which comprises passing the gas and the slurry that results from the interaction of the gas and solution through a sexies oi tanks, withdrawing from each tank in the series and returning thereto through a Venturi tube eductor acertain amount of slurry intimately admixed with a considerably larger volume of gas withdrawn from the tank by the eductor, and withdrawing from the last tank in the series an amount of slurry substantially equivaient to the amount of solution introduced into the iirst tank in the series.

3. The method of producing precipitates by the reaction of a gas with a solution which comprises passing the gas and the slurry that results from the interaction of the gas and solution through a series of tanks, withdrawing a certain amount of slurry from each tank in the series and returning a part of the withdrawn slurry intimately admixed with gas back into that tank 4o and conveying the remainder of the withdrawn slurry intimately admixed with gas to the next succeeding tank in the series, and withdrawing from the last tank in the series an amount of slurry substantially equivalent to the amount of solution introduced into the ilrst tank in the series.

4. The method of producing precipitates by the reaction oi.' a gas with a solution which compsespassingthegasandtheslurrythatreailtso from the interaction of the gas and solution through a series of tanks, withdrawing a certain amount of slurry fromA each tank in the series and returning thereto through a Venturi tube eductor a part of the withdrawn slurry in- 'l timately admixed with a considerably larger volume of gas withdrawn from that tank by the eductor and conveying to the next succeeding tank in the series through a Ventm'i tube eductor the remainder of the withdrawn slurry intimately admixed with gas withdrawn from that tank by the eductor, and withdrawing from the last tank in the series an amount of slurry substantially equivalent to the amoimt of solution introduced into the rst tank in the Series. 55`

5. The method of producing precipitates by the reaction of a gas with a solution which comprises passing the gas and the slurry that results from the-interaction of the gas and solution through a series of tanks, introducing into the iirst tank in the series through a Venturi tube eductor fresh solution intimately admixed with a considerably larger volume of gas withdrawn from thattank by the eductor, withdrawing a certain amount of slurry from each tank in the series and returning. n--nart of the wiuianiwn siurry inu- 2 mately admixed with gas back into that tank and conveying theremainder of the withdrawn slurry Aintimately admixed with gas to the next succeed'- ing tank in the series,` and A'withdrawing fromthe last-,tank in the series an amount of slurry substantially equivalent to the amount of fresh solu` tion introducedinto the first tank in the series.

6. The method of producing precipitates by.`

the reaction o f a gas with a solution which comprises .passing the gas and the slurry that results from the interaction of the gas and solution through a series of tanks.' introducing-into the rst tank in the series through a Venturi Vtubei series and returning thereto through a Venturi tube eductor a part of the withdrawn slurry intimately admixed with a.A considerably larger volume of gas withdrawn from that tank by the eductor and conveying to the next succeeding tank in the series through a VVenturi tube eductor the-remainder of the withdrawn slurry intimately admixed with gas withdrawn from that'tankbythe eductor, and withdrawing from the last tank in the series an amount of slurry substantially equivalent to the amount of fresh solution introduced into the first tankin th series. l

'1. The method of producing precipitates by the reaction of a gas with a solution which com.- prises passing the gas-and the slurry that results from the interaction -of the gas and solution through a series of tanks, lwithdrawing a certain amount of slurry from each tank in theA series and returninga part of the withdrawn slurry intimately admixed with gas back into that tank and conveying the remainder of the withdrawn slurry intimately admixed Vwith gas to the next succeeding tank in theA series, regulatingthe relative amounts of the slurry withdrawnfrom each tank which are returned to that tank and con- Y veyed to the next succeeding tank, and withdrawing from the last tank in the series an amount of slurry substantially equivalent to the amount of solution introduced into .the rst tank in the series.

' 8. The method of producing precipitates by the reactiohof a gas withl a solution which comprises `passing the gas and the slurry that results from the interaction of :the gas and solution through a series of tanks, withdrawing a certain amount of slurry from each tank in the series andreturning thereto through a Venturi tube eductor a part of the withdrawn slurry intimately admixed with a considerably larger volume of gas with drawn from that tank by the eductor and conveying to the next succeeding tank in the series through a Venturi tube eductor the remainder of the withdrawn slurry intimately admixed 'with gas withdrawn from that tank by the eductor, regulating the relative amounts of the slurry withdrawn from each tank which are returned to that tank and conveyed to the next succeeding tank, and withdrawing from the last tank in the series an amount of slurry substantially equivalent to the amount of solution introduced into the first tank in the series.

9. The method of producing precipitates by the reaction of a gas with a solution which comprises mixing the solution with a relatively much larger volume of thel gas in an eductor discharging into an atmosphere of the gas in a closed tank partly aoadsas nnen with slurry resulting from the interaction oi the solution and gas, and recirculating a certain amount of said slurry by mixing the slurry with a-relatively much'larger'volume of the gas in a second eductor also discharging into the atmos phere of gas in said tank; 4

10. The method of producing precipitates by the reaction of agas with a solution which comprises.v

- mixing the solution in a Venturi tube eductor with a relatively much larger volume o i the gas withdrawnby the eductor from a closed tank partly filled with slurry resulting from the interaction of .the solution and gas, and discharging the slurry resulting from the mixing in the eductor of the solution and gas into an atmosphere of gas above tneslurry in said tank.y

11. The method of producing precipitates by the reaction of a gas with a solution which comprises mixing the solution in a Venturi tube eductor with a relatively much larger volume of vthe gas withdrawn'by the eductor from a closed tank partly iilled with slurry resulting from the interaction of the solution and gas,4 discharging the slurry resulting from the mixing in the eductor of the solution and gas into an atmosphere of gas above the slurry in said' tank, and recirculating a certain amount ofthe slurry in said tank by mixing the recirculating slurry in a second Venturi tube eductor, also discharging into the atmosphere of gas in saidftank, with a relatively 30 much larger volume of the gas withdrawn by the eductor from the tank.

12. rll'he method of producing precipitates by the reaction of a gas with a solution which comprises passing the gasand slurry that results from the interaction of the gas and solution countercurrently through a seriesl of closed tanks, mixing in a Venturi tube eductor, discharging into the atmosphere of gas above the slurry in the rst tank in-said series, fresh solution with a relatively much larger volume of the gas withdrawn from the tank by the eductor, withdrawing a certain amount of slurry from each tank in the series and returning a part of the withdrawn slurry mixed with gas withdrawn from the same tank back into that tank through a -Venturi tube eductor discharging into the atmospherecf gas in the tank and conveying the remainder of the withdrawn slurry to the next succeeding tank in the series through a similar Venturi tube eductor,V

' with slurry resulting from. the interaction of the solution and gas.

14. The improvement in the precipitation of zinc sulfide by the action of hydrogen sulfide gas 65 upon an aqueous solution of a zinc salt which comprises mixing the slurry that results from the partial interaction of said solution and gas with a relatively much larger volume of hydrogen mosphere of hydrogen sulde gas in a closed tank partly lled with slurry.

15. 'I he improvement in the precipitation of zinc sulfide by the action oi hydrogen sulfide gas upon an aqueous solution of a zinc salt which Y sulfide gas in an eductor discharging into an at- 0 comprises the aqueous solution oi' 'a relatively much larger volume of hydrogen suliide gasinaneductordischargingintoanatmosphere ofnydmgensulndegasmaclednkparuy iilled with slurry resulting from the interaction or the solution andgas, and recirculating a certain' amount of said slurry by mixing the slurry with a relatively much larger volume of hydrogen `sulilde gas in a second eductor discharging into hydrogen suliide gas in said 1 upon an aqueous solution of a zinc salt which comprises mixing the aqueous solution in a Venturi tube eductor with a relatively much larger volume of lrvdrogen suldegas withdrawn by the eductoriromaciosedtankpartlylledwithslurry resulting from the interaction of said solution and gas, and discharging the slurry resulng from the mixing in the eductor of said solution and gas into an atmosphere oi hydrogen suliide gas above theshn'ryinsaid tank.

17. The improvement in the precipitation oi zinc suliide by the action of hydrogen suliide gas upon an aqueous solution of a zinc salt which comprises mixing the aqueous solutionin a Venturi tube eductor with a relatively much larger volume o! hydrogen sulfide gas withdrawn by the eductor from a closed tank partly`iilled with slurry resulting from the interaction of said solution and gas, discharging the slurry resulting from the mixing in the eductor of said solution and gas into an atmosphere oi hydrogen sulde gas above the slurry in said tank, and recirculating a certain amount of the slurry in said tank by mixing the recirculating slurry in a second Venturi tube eductor, also discharging into the atmosphere of hydrogen sulilde gas in said tank, with a relativeLv much larger volume o! hydrogen suliide gas withdrawn by the eductor from the tank.

18. The improvement in the precipitation of zinc sulfide by the action of hydrogen sulde upon an aqueoussolution oi' a zinc salt which comprises introducing the solution into a tank through an eductor operating to withdraw from the tank and mix with the entering solution a relatively much larger volume of hydrogen suliide, and conveying slurry from said tank to a second tank through an eductor operating to withdraw from the second tank and mix with the entering slurry a relatively much larger volume of hydrogen sulfide.

19. The improvement in the precipitation of xine sulfide by the action oi.' hydrogen sulfide upon an aqueous solution o! a zinc salt which,

comprises introducing the solution into a tank through an eductor operating4 to withdraw from the tank and mix with the entering solution a relatively much largervolume of hydrogen sulfide, conveying slurry -irom said tank to a second tank through an eductor operating to withdraw from the second tank and mix with the entering slurry a relatively much larger volume oi hydrogen sulfide, and circulating the slurry in each 20. The method of producing a precipitate of zinc sulde by the reaction of hydrogen suliide gas with a solution o! a zinc salt which comprises passing the gas and the slurry that results from the interaction of the hydrogen sulnde and zinc 5 salt solution countercurrently through a series ot tanks, withdrawing a certain amount oi.' slurry from each tank in the series and returning' a part of the withdrawn slurry intimately admixed with gas back into that tank and conveying the lremainder ci' the withdrawn slurry intimately admixed with gas to the next succeeding tank in the series, regulating the relative amounts of the slurry withdrawn from each tank which are returned to that tank and conveyed to the next succeeding tank, and withdrawing from the last tank in the series an amount of slurry substantially equivalent to the amount o! solution introduced into the nrst tank in the series.-

21. Ihe method of producing a precipitate of zu zinc suliide by the reaction of an aqueous solution oi a zinc salt with hydrogen sulfide gas which comprises progressively conducting a slurry ot the zinc sulilde precipitate resulting from the interaction of the aqueous solution of zinc salt and hydrogen sulfide gas through a series of tanks, introducing into and withdrawing from each tank zinc sulde slurry in such relative amounts' that a substantially constant level of slurry is maintained in each tank, and providing 3'0 an atmosphere of hydrogen suliide gas above and in contact with the body of zinc sulfide slurry in each tank.

22. The method oi producing a precipitate of zinc suliide by the reaction of an aqueous solu- $5 tion or a zinc salt with hydrogen suliide gas which comprises progrsively conducting a slurry of the zinc suliide precipitate resulting from the interactionof the aqueous solution or zinc salt and hydrogen sulde gas through 9.40 series oi.' tanks, introducinginto and withdrawing from each tank zinc suliide slurry in such relative amounts that a substantially constant level of slurry is maintained in each tank, and

progressively advancinga supply of hydrogen 45 sulflde gas through said tanks in a direction generally countercurrent to the direction of passage of the zinc sulfide slurry through the tanks.

23. The method of producing a precipitate of zinc sulilde by the reaction of an aqueous solution of a zinc salt with hydrogen suliide gas which comprises progressively conducting a slurry of the zinc sulde precipitate resulting from the interaction of the aqueous solution oi zinc salt andhydrogen suliide gas through a5!! series of tanks, introducing into and withdrawing from each tank zinc sulilde slurry in such relative amounts that a substantially constant level of slurry is maintained in each tank, and progressively' advancing a supply or hydrogen 60 sulde gas through said tanks to provide an at mosphere of the gas above and in contact with thebodyofzincsulildeslurryineachtank,the zinc sulfide slin'ry being introduced into each tank by showering the same through said atmosphere oi.' hydrogen sulnde gas to insure intimate contact between the slurry and the gas.

ARNELMYHRENQ BYRON MARQUIS. 

